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At least 163 records · Page 9

Well-Defined Iron Sites in Crystalline Carbon Nitride

Carbon nitride materials can be hosts for transition metal sites, but Mössbauer studies on iron complexes in carbon nitrides have always shown a mixture of environments and oxidation states. Here we describe the synthesis and characterization of a crystalline carbon nitride with stoichiometric iron sites that all have the same environment. The material (formula C 6 N 9 H 2 Fe 0.4 Li 1.2 Cl, abbreviated PTI/FeCl 2 ) is derived from reacting poly(triazine imide)·LiCl (PTI/LiCl) with a low-melting FeCl 2 /KCl flux, followed by anaerobic rinsing with methanol. X-ray diffraction, X-ray absorption and Mössbauer spectroscopies, and SQUID magnetometry indicate that there are tetrahedral high-spin iron(II) sites throughout the material, all having the same geometry. As a result, the material is active for electrocatalytic nitrate reduction to ammonia, with a production rate of ca. 0.1 mmol cm –2 h –1 and Faradaic efficiency of ca. 80% at −0.80 V vs RHE.

Anions↗

Photochemical Tungsten–Carbon Bond Cleavage in Bicyclic Tungstacyclopentanes

W(NCPh 3 )(OSiPh 3 ) 2 (C7H 12 ) (1) and W(NAd)(OSiPh 3 ) 2 (C 7 H 12 ) (2) undergo photochemical α-hydrogen abstraction to form alkylidenes. Transient absorption studies suggest that fast W–C homolysis precedes thermal α-hydrogen abstraction. Radical trapping experiments in the presence of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) support formation of an alkyl radical in these reactions. DFT calculations of models of 1 and 2 are also consistent with formation of W(V)-alkyl-radical intermediates that ultimately abstract an α-hydrogen to form the alkylidene. This article provides evidence for W–C bond cleavage in reac-tions that convert catalytically inactive d 0 tungstacyclopentanes into metathesis-active alkylidenes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic realization of emergent high-dimensional optical vortices

The dimensionality of vortical structures has recently been extended beyond two dimensions, providing additional topological complexity and robustness for high-capacity information processing and turbulence control. The generation of high-dimensional vortical structures has mostly been demonstrated in classical systems through the complex interference of fluidic, acoustic, or electromagnetic waves. However, natural materials rarely support three- or higher-dimensional vortical structures and their physical interactions. Here, we experimentally demonstrate a high-dimensional gradient thickness optical cavity (GTOC) in which the optical coupling of planar metal-dielectric multilayers implements topological interactions across multiple dimensions. At non-trivial topological phases, high-dimensional GTOC induces high-dimensional vortical structures in generalized parameter space in three, four dimensions, and beyond. These emergent high-dimensional vortical structures are observed under electro-optic tomography as optical vortex dynamics in two-dimensional real-space, employing the optical thicknesses of dielectric layers as synthetic dimensions. Our findings hold significant promise for emulating high-dimensional physics and developing active topological photonic devices.

36 MATERIALS SCIENCE↗

Solid Waste Release Calculations for the Composite Analysis Baseline Assessment

The purpose of the Hanford Site Composite Analysis (CA) is to provide an estimate of the cumulative radiological impacts from active and planned low-level radioactive waste disposals and other potentially interacting radioactive waste disposal sources that will remain following Hanford Site closure. The need for a waste form release model addressing multiple solid waste forms is documented in CP-60410, Hanford Site Composite Analysis Technical Approach Description: Waste Form Release.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Material Discovery and High Throughput Exploration of Ru Based Catalysts for Low Temperature Ammonia Decomposition

High throughput experimentation has the capability to generate massive, multidimensional datasets, allowing for the discovery of novel catalytic materials. Here, we show the synthesis and catalytic screening of over 100 unique Ru-Metal-K based bimetallic catalysts for low temperature ammonia decomposition, with a Ru loading between 1–3 wt% Ru and a fixed K loading of 12 wt% K, supported on γ-Al2O3. Bimetallic catalysts containing Sc, Sr, Hf, Y, Mg, Zr, Ta, or Ca in addition to Ru were found to have excellent ammonia decomposition activity when compared to state-of-the-art catalysts in literature. Furthermore, the Ru content could be reduced to 1 wt% Ru, a factor of four decrease, with the addition of Sr, Y, Zr, or Hf, where these secondary metals have not been previously explored for ammonia decomposition. The bimetallic interactions between Ru and the secondary metal, specifically RuSrK and RuFeK, were investigated in detail to elucidate the reaction kinetics and surface properties of both high and low performing catalysts. The RuSrK catalyst had a turnover frequency of 1.78 s−1, while RuFeK had a turnover frequency of only 0.28 s−1 under identical operating conditions. Based on their apparent activation energies and number of surface sites, the RuSrK had a factor of two lower activation energy than the RuFeK, while also possessing an equivalent number of surface sites, which suggests that the Sr promotes ammonia decomposition in the presence of Ru by modifying the active sites of Ru.

McCullough, Katherine (ORCID:0000000197525740)↗

Promiscuous G-protein activation by the calcium-sensing receptor

The human calcium-sensing receptor (CaSR) detects fluctuations in the extracellular Ca 2+ concentration and maintains Ca 2+ homeostasis. It also mediates diverse cellular processes not associated with Ca 2+ balance. The functional pleiotropy of CaSR arises in part from its ability to signal through several G-protein subtypes. Here, we determined structures of CaSR in complex with G proteins from three different subfamilies: G q , G i and G s . We found that the homodimeric CaSR of each complex couples to a single G protein through a common mode. This involves the C-terminal helix of each Gα subunit binding to a shallow pocket that is formed in one CaSR subunit by all three intracellular loops (ICL1–ICL3), an extended transmembrane helix 3 and an ordered C-terminal region. G-protein binding expands the transmembrane dimer interface, which is further stabilized by phospholipid. The restraint imposed by the receptor dimer, in combination with ICL2, enables G-protein activation by facilitating conformational transition of Gα. We identified a single Gα residue that determines G q and G s versus G i selectivity. The length and flexibility of ICL2 allows CaSR to bind all three Gα subtypes, thereby conferring capacity for promiscuous G-protein coupling.

36 MATERIALS SCIENCE↗

Influence of CaO/FeO ratio on the formation mechanism and properties of alkali-activated Fe-rich slags

Highlights: • Effect of the CaO/FeO molar ratio in alkali-activated Fe-rich slags is unraveled. • Low CaO/FeO molar ratios enhance the early kinetics and compressive strength. • Reaction extent and strength further increase with higher CaO/FeO ratio after 7 days. • Fe{sup 2+}-trioctahedral layers of the binder are hydroxylated and in a silicate phase. • The final strength is determined by the influence of Ca on the reaction products. In the search for CO{sub 2} mitigating cement technologies, alkali-activated Fe-rich slags present a possible alternative. The influence of the chemical composition of the synthetic Fe-silicate slag on the reaction mechanisms is assessed by varying the CaO/FeO molar ratio. The alkali-activated Fe-rich slags consist of trioctahedral layers that are shown to be hydroxylated and in contact with silicates, in a similar way to phyllosilicate minerals. The formation of this phyllosilicate-like structure is hindered during the first days for samples with high CaO/FeO ratios, because of the partial incorporation of Ca in the trioctahedral layers. At later ages, the samples with higher CaO/FeO ratios gain in reaction extent, to exceed the reaction extent of low CaO/FeO ratios at 28 days and beyond. The increase in compressive strength is even more pronounced than the effect on the reaction extent, which underlines the importance of Ca on the inherent strength of the binding phases.

36 MATERIALS SCIENCE↗

Storms Are an Important Driver of Change in Tropical Forests

Tropical forest dynamics and composition have changed over recent decades, but the proximate drivers of these changes remain unclear. Investigations into these trends have focused on increasing drought stress, CO 2 , temperature, and fires, whereas convective storms are generally overlooked. We argue that existing literature provides clear support for the importance of storms as drivers of forest change. We reanalyze the largest plot-based study of tropical forest carbon dynamics to show that lightning frequency—an indicator of storm activity—strongly predicts forest carbon storage and residence time, and its inclusion improves model fit and weakens evidence for the effects of high temperatures. Convective storm activity has increased 5%–25% per decade over the past half century. Extrapolating from historic trends, we estimate that storms likely contribute ca. 50% of the reported increases in biomass mortality across Amazonia, with all realistic combinations of assumptions indicating a possible range of 12%–118%. Spatial variation in storm activity shows weak relationships with drought, demonstrating that forests can experience high drought stress, high storm activity, or both. Accordingly, we hypothesise that convective storms are among the most important drivers of tropical forest change, and as such, they require significant research investment to avoid misguiding science, policy, and management.

biomass carbon↗

Unlocking the Potential of A-Site Ca-Doped LaCo 0.2 Fe 0.8 O 3-δ : A Redox-Stable Cathode Material Enabling High Current Density in Direct CO 2 Electrolysis

Massive carbon dioxide (CO 2 ) emission from recent human industrialization has affected the global ecosystem and raised great concern for environmental sustainability. The solid oxide electrolysis cell (SOEC) is a promising energy conversion device capable of efficiently converting CO 2 into valuable chemicals using renewable energy sources. However, Sr-containing cathode materials face the challenge of Sr carbonation during CO 2 electrolysis, which greatly affects the energy conversion efficiency and long-term stability. Thus, A-site Ca-doped La1– x CaxCo 0.2 Fe 0.8 O 3-δ (0.2 ≤ x ≤ 0.6) oxides are developed for direct CO 2 conversion to carbon monoxide (CO) in an intermediate-temperature SOEC (IT-SOEC). With a polarization resistance as low as 0.18 O cm 2 in pure CO 2 atmosphere, a remarkable current density of 2.24 A cm –2 was achieved at 1.5 V with La 0.6 Ca 0.4 Co 0.2 Fe 0.8 O 3-δ (LCCF64) as the cathode in La 0.8 Sr 0.2 Ga 0.83 Mg 0.17 O 3-δ (LSGM) electrolyte (300 µm) supported electrolysis cells using La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) as the air electrode at 800 °C. Furthermore, symmetrical cells with LCCF64 as the electrodes also show promising electrolysis performance of 1.78 A cm –2 at 1.5 V at 800 °C. In addition, stable cell performance has been achieved on direct CO 2 electrolysis at an applied constant current of 0.5 A cm –2 at 800 °C. The easily removable carbonate intermediate produced during direct CO 2 electrolysis makes LCCF64 a promising regenerable cathode. The outstanding electrocatalytic performance of the LCCF64 cathode is ascribed to the highly active and stable metal/perovskite interfaces that resulted from the in situ exsolved Co/CoFe nanoparticles and the additional oxygen vacancies originated from the Ca 2 Fe 2 O 5 phase synergistically providing active sites for CO 2 adsorption and electrolysis. Here this study offers a novel approach to design catalysts with high performance for direct CO 2 electrolysis.

30 DIRECT ENERGY CONVERSION↗

Material‐Driven Neuronal Oscillators and Filters via Active Reactance in CC‐NDR and VC‐NDR Electro‐Thermal Memristors

The continued scaling of artificial intelligence and telecommunications hardware is increasingly constrained by the power, bandwidth, and area limitations of transistor-based circuits. Neuromorphic processor units, analog oscillators, and active inductors and capacitors rely on complex multi-transistor architectures restricting material choices and incurring energy and footprint overhead. Here, we show that active reactance in electro-thermal memristors provides an intrinsic, material driven route to neuronal oscillator dynamics and signal processing. Using a physics-based compact modeling framework, we bridge negative differential resistance (NDR) and bias-tunable reactance, which underlies spiking dynamics in electro-thermal memristors. Memristors with negative temperature coefficients of resistance (TCR) manifest current-controlled (CC-) NDR and act as active inductors, thus generating spiking above a critical circuit capacitance; whereas memristors with positive TCR manifest voltage-controlled (VC-) NDR and active capacitance, leading to spiking above a critical inductance. By creating a compact model for La 0.7 Ca 0.3 MnO 3 as a representative VC-NDR material and comparing it with LaCoO 3 manifesting CC-NDR, we explain the physical origins of their distinct current-voltage characteristics, reactive phase shifts and consequent spiking behaviors. Finally, we demonstrate tunable filtering enabled by the active reactance of electro-thermal memristors, establishing them as a compact hardware platform for neuronal oscillator functionality and integrated filtering beyond conventional CMOS.

active reactance↗

Searching for Active Low-mass Stars in the CMa Star-forming Region: Multi-band Photometry with T80S

An exotic environment surrounds the young stellar groups associated with the Canis Major (CMa) OB1/R1 region, which probably was formed under feedback from at least three supernova events having occurred a few million years ago. We use astrometric data from the Gaia-DR2 to confirm the membership of the stars in CMa R1, based on proper motion and parallax, which revealed 514 new members and candidates. The mean age of 5 Myr estimated from the color–magnitude diagram characterizes the sources as likely pre-main-sequence candidates. In total, a sample of 694 stars detected with the T80-South telescope was analyzed according to different color–color diagrams, which were compared with theoretical colors from evolutionary models, aiming to reveal the objects that exhibit color excess due to accretion processes. Accretion and magnetic activity were also explored on the basis of empirical flux–flux relation, such as F {sub 660} and F {sub 861} that are related to Hα and Ca ii triplet emission, respectively. A low fraction (∼3 percent) of the sample have Hα excess and other colors expected for stars exhibiting chromospheric activity. The number of Class I and Class II objects, identified by the infrared (Wide-field Infrared Survey Explorer) colors, indicates a disk fraction of ∼6 percent, which is lower than that expected for stellar clusters with a similar age. Such a large sample of objects associated with CMa R1 without evidences of circumstellar accretion can be interpreted as a lack of disk-bearing stars, unusual for young star-forming regions. However, this may be explained as the result of supernova events.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

New principles of self‐organization created through the interplay of DNA condensates, microtubules, and motors

Bioinspired design—which holds great promise for a new generation of materials that are robust to defects, scalable under green manufacture, environmentally responsive, and programmably reconfigurable—requires mastery over molecular self-organization. Yet, from its specific mechanisms to most general architectures, the principles governing self-organization remain poorly understood and not even fully enumerated. For living systems, one obvious architectural principle is the modular reuse of a few simple molecular components in myriad combinations to achieve more complex phenomena. For example, the mechanical tasks of a cell are driven by the nonequilibrium dynamics of cytoskeletal filaments and molecular motors—the same filaments and motors, reprogrammed by a variety of modulators, perform tasks ranging from cell movement to division. Similarly, many compartmentalization tasks are performed by liquid-like condensates of simple components, which act as membraneless organelles to localize particular molecules in space and time (e.g. for gene regulation or RNA processing). In a few cases, condensates combine and interact with the cytoskeleton to create still more complex phenomena, e.g. the nucleation of microtubule asters from the centrosome (a protein condensate) to form the mitotic spindle during cell division. Very little is known about the fundamental mechanisms of such filament-plus-condensate phenomena. Despite few examples, the landscape of behaviors that can be achieved through the combination of condensates, filaments, and motors appears vast. However, exploration has been hindered by a lack of systems that have sufficiently programmable and dynamically tunable interactions between component condensates, filaments, and motors. We proposed to combine programmable DNA condensates, filamentous microtubules, and light-controlled motors into self-organizing systems whose principles go beyond those that have been observed in nature. In one limit, our systems will use microtubules and motors to create the molecular analog of a network of roads, which will organize droplets of DNA condensates capable of carrying molecular cargo. DNA condensates coupled to motors will flow from one microtubule aster hub to another, with their direction and timing controlled by DNA circuits. In another limit, microtubules will swim through bulk DNA condensates and exhibit strong interactions with boundaries between different types of condensates. Microtubule swimmers will reflect, get trapped, or refract at boundaries, under a mechanical analog of the classical optical index of refraction. DNA condensates having different mechanical indexes of refraction will be used to construct the analog of optical lenses, so that microtubule swimmers can be manipulated like light—collimated, diffracted, focused, and sorted based on properties analogous to wavelength. These two limits define two new architectures, within which multiple new mechanistic principles for self-organization will be discovered and explored. To explore these architectures, the motor-based coupling between DNA condensates and filaments will be controlled in time and space through the use of opto-proteins that create reversible links between DNA condensates and motors upon illumination. For each principle of interest, patterns of light will create virtual experiments by defining patterns of activity where DNA condensates walk along filaments, or filaments swim through condensates, and patterns of inactivity which will serve either as controls, or as boundary conditions vital to create the desired phenomena. This research serves the goals of Basic Energy Sciences Biomolecular Material Program by elucidating the principles by which the emergent, nonequilibrium behavior of collections of DNA condensates, motors, and microtubules can be programmed by environmental light patterns to create complex motion and materials transport. Because DNA condensates can be readily coupled to virtually any high performance nanomaterial, from carbon nanotubes, to metal nanoparticles, to light harvesting systems, this work provides a path to the construction, self-maintenance and reconfiguration of materials relevant to the Department of Energy.

60 APPLIED LIFE SCIENCES↗

Quantitative DNA Stable Isotope Probing Identifies Active Microorganisms Assimilating Volatile Fatty Acids in Full-Scale Enhanced Biological Phosphorus Removal Processes

Enhanced biological phosphorus removal (EBPR) systems often rely on exogenous carbon sources, such as volatile fatty acids (VFAs), to achieve higher P removal. Here, we employed DNA quantitative stable isotope probing (qSIP) using two VFAs, acetate and propionate, in cyclic anaerobic/aerobic incubations to assess their effects on P cycling and microbial activity with biomass from two full-scale EBPR water resource-recovery facilities that utilize VFA addition. We found that anaerobic VFA uptake preferences differed within known groups of PAOs, such as Candidatus Accumulibacter and Tetrasphaera-affiliated members (e.g., Ca. Phosphoribacter), between the two biomasses. The combination of qSIP with metagenomics identified isotopically labeled phages that were linked to active PAOs, highlighting their potential roles in modulating EBPR community composition and activity. The highest levels of anaerobic labeling from acetate were in genomes belonging to Saccharimonadales and Rickettsiales, which are generally host-associated with bacteria and eukaryotes, respectively. Furthermore, this finding highlights the possibility of cross-feeding between PAO hosts and their parasites or predators, as well as the role of so-far uncharacterized organisms participating in carbon cycling under EBPR conditions. Collectively, these results expand our understanding of the ecological interactions involved in communities anaerobically uptaking VFAs and cycling P that are central to EBPR.

Polyphosphate accumulating organisms↗

Exploring Ca–Ce–M–O (M = 3d Transition Metal) Oxide Perovskites for Solar Thermochemical Applications

Solar thermochemical (STC) processes hold promise as efficient ways to generate renewable fuels, fuel precursors, or chemical feedstocks using concentrated sunlight. Specifically, one actively researched approach is the two-step STC cycle, which uses a redox-active, off-stoichiometric, transition-metal oxide material to split water and/or CO 2 , generating H 2 and/or CO, respectively, or syngas (a combination of H 2 and CO). Identifying novel metal oxides that yield larger reduction extents (practically achievable off-stoichiometries) than the state-of-the-art CeO 2 is critical. Here, we explore the chemical space of Ca–Ce–M–O (M = 3d transition metal, except Cu and Zn) metal oxide perovskites, with Ca and/or Ce occupying the A site and M occupying the B site within an ABO 3 framework, as potential STC candidates. We use density functional theory (DFT)-based calculations and systematically evaluate the oxygen vacancy (VaO) formation energy (≈ enthalpy of reduction in an STC cycle), electronic properties, thermodynamic stability of CaMO 3 , CeMO 3 , and Ca 0.5 Ce 0.5 MO 3 perovskites, and the VaO formation energy within Ca 0.5 Ce 0.5 Ti 0.5 Mg 0.5 O 3 perovskite. We consider only Ca and/or Ce on the A site because of their similar size and the potential redox activity of Ce 4+ . If both Ce and M exhibit simultaneous reduction with Va O formation, the resulting perovskite could exhibit a larger entropy of reduction than a single cation reduction. The increased entropy produces increased reduction for fixed temperature, partial pressure of oxygen, and reduction enthalpy, and therefore increased STC efficiency. Importantly, we identify Ca 0.5 Ce 0.5 MnO 3 , Ca 0.5 Ce 0.5 FeO 3 , and Ca 0.5 Ce 0.5 VO 3 to be promising candidates based on their Va O formation energy and thermodynamic (meta)stability. Moreover, based on our calculated on-site magnetic moments, electron density of states, and electron density differences between pristine and defective structures, we find Ca 0.5 Ce 0.5 MnO 3 to exhibit simultaneous reduction of both Ce 4+ (A-site) and Mn 3+ (B-site), highlighting a particularly promising candidate for STC applications with a predicted higher entropy of reduction than CeO 2 . Lastly, we extract metrics that govern the trends in Va O formation energies, such as standard reduction potentials, and provide pointers for further experimental and theoretical studies, which will enable the design of improved materials for the STC cycle.

14 SOLAR ENERGY↗

Bioinspired Design of Dissipative Self-Assembly of Active Materials (Final Technical Report)

The major objective of this DOE-funded research program was to establish general, experimentally validated design principles for dissipative, out-of-equilibrium self-assembly of synthetic active materials. In living systems, structures such as actin filaments and microtubules are maintained far from thermodynamic equilibrium through continuous energy consumption. This persistent nonequilibrium operation enables functions including adaptability, self-healing, directed motion, and force generation—properties that are largely absent in traditional equilibrium soft materials.

36 MATERIALS SCIENCE↗

Dynamic basis of supercoiling-dependent DNA interrogation by Cas12a via R-loop intermediates

The sequence specificity and programmability of DNA binding and cleavage have enabled widespread applications of CRISPR-Cas12a in genetic engineering. As an RNA-guided CRISPR endonuclease, Cas12a engages a 20-base pair (bp) DNA segment by forming a three-stranded R-loop structure in which the guide RNA hybridizes to the DNA target. Here we use single-molecule torque spectroscopy to investigate the dynamics and mechanics of R-loop formation of two widely used Cas12a orthologs at base-pair resolution. We directly observe kinetic intermediates corresponding to a ~5 bp initial RNA-DNA hybridization and a ~17 bp intermediate preceding R-loop completion, followed by transient DNA unwinding that extends beyond the 20 bp R-loop. The complex multistate landscape of R-loop formation is ortholog-dependent and shaped by target sequence, mismatches, and DNA supercoiling. A four-state kinetic model captures essential features of Cas12a R-loop dynamics and provides a biophysical framework for understanding Cas12a activity and specificity.

59 BASIC BIOLOGICAL SCIENCES↗

Temperature dependence of nitrate-reducing Fe(II) oxidation by Acidovorax strain BoFeN1 – evaluating the role of enzymatic vs. abiotic Fe(II) oxidation by nitrite

ABSTRACT Fe(II) oxidation coupled to nitrate reduction is a widely observed metabolism. However, to what extent the observed Fe(II) oxidation is driven enzymatically or abiotically by metabolically produced nitrite remains puzzling. To distinguish between biotic and abiotic reactions, we cultivated the mixotrophic nitrate-reducing Fe(II)-oxidizing Acidovorax strain BoFeN1 over a wide range of temperatures and compared it to abiotic Fe(II) oxidation by nitrite at temperatures up to 60°C. The collected experimental data were subsequently analyzed through biogeochemical modeling. At 5°C, BoFeN1 cultures consumed acetate and reduced nitrate but did not significantly oxidize Fe(II). Abiotic Fe(II) oxidation by nitrite at different temperatures showed an Arrhenius-type behavior with an activation energy of 80±7 kJ/mol. Above 40°C, the kinetics of Fe(II) oxidation were abiotically driven, whereas at 30°C, where BoFeN1 can actively metabolize, the model-based interpretation strongly suggested that an enzymatic pathway was responsible for a large fraction (ca. 62%) of the oxidation. This result was reproduced even when no additional carbon source was present. Our results show that at below 30°C, i.e. at temperatures representing most natural environments, biological Fe(II) oxidation was largely responsible for overall Fe(II) oxidation, while abiotic Fe(II) oxidation by nitrite played a less important role.

Microbiology↗

Carbonation of Alkaline Earth Metal Hydroxides: Structure across Nano- to Mesoscales

The conversion of gaseous CO 2 into a solid constitution through mineralization is an active area of carbon capture, and alkaline earth metal hydroxides (M(OH) 2 , M = Ca 2+ , Mg 2+ ) are frontrunners in this area. As model systems, nanolime samples are excellent templates for the study of this reaction. Here, we have examined these under ambient pressure conditions with controlled humidity and CO 2 . Utilizing a broad range of analytical methods, we first established the purity and structures of the selected materials. We then examined the structural changes due to carbonation, using infrared spectroscopy, X-ray scattering, and neutron scattering. The resulting structural changes are resolved from nanoscale to mesoscale and from early-stage to late-stage carbonation. Ca(OH) 2 and Mg(OH) 2 are found to behave quite differently. As expected from prior work, the carbonation of Ca(OH) 2 is kinetically favored. Further, our structure studies suggest this is due to a facile reaction at the fractal interface of the particles. From early- to late-stage carbonation, there is a consistent increase in the fractal roughness. This is in contrast to Mg(OH) 2 where the same surface evolves into a smooth conformal coating. For this material the major reacting component is at the mesoscale, suggesting globular particle growth or evolving macro-porosity. Because neutron scattering is sensitive to hydrogen content, we expected a significant change as M(OH) 2 evolves to MCO 3 . Such a change is found for Ca(OH) 2 but not for Mg(OH) 2 , providing evidence for the formation of hydrated carbonates for the later material. The formation of a conformal layer along with water-rich carbonate formation is an impediment to the use of Mg(OH) 2 for carbon capture. For energy-efficient carbon capture, it would be desirable to enhance carbonation rates for Mg(OH) 2 , and one possible route would be the use of anhydrous fluids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗